Removal of xylenol orange from its aqueous solution using SDS self-microemulsifying systems: optimization by Box–Behnken statistical design

The aim of present study was to develop and evaluate sodium dodecyl sulfate (SDS) self-microemulsifying systems (SMES) for the removal of an anionic dye xylenol orange (XO) from its bulk aqueous media via liquid–liquid adsorption. The composition of SDS SMES was optimized by Box–Behnken statistical design for the maximum removal of XO from its aqueous solution. Various SDS formulations were prepared by spontaneous emulsification method and characterized for thermodynamic stability, self-microemulsification efficiency, droplet size, and viscosity. Adsorption studies were conducted at 8, 16, and 24 h by mixing small amounts of SDS formulations with relatively large amounts of bulk aqueous solution of XO. Droplet size and viscosity of SDS formulations were significantly influenced by oil phase concentration (triacetin), while surfactant concentration had little impact on droplet size and viscosity. However, the percentage of removal of XO was influenced by triacetin concentration, surfactant concentration, and adsorption time. Based on lowest droplet size (35.97 nm), lowest viscosity (29.62 cp), and highest percentage of removal efficiency (89.77 %), formulation F₁₄, containing 2 % w/w of triacetin and 40 % w/w of surfactant mixture (20 % w/w of SDS and 20 % w/w of polyethylene glycol 400), was selected as an optimized formulation for the removal of XO from its bulk aqueous media after 16 h. These results indicated that SDS SMES could be suitable alternates of solid–liquid adsorption for the removal of toxic dyes such as XO from its aqueous solution through liquid–liquid adsorption.     

Influence of surfactants and polymeric adjuvants on physicochemical properties, droplet size spectra and deposition of fenitrothion and Bacillus thuringiensis formulations under laboratory conditions

The effect of two surfactants and two polymeric adjuvants on droplet size spectra and deposition patterns of nine spray formulations was investigated following atomization in a laboratory chamber using a spinning disc atomizer that can produce a narrow droplet size spectrum. Spray droplets were sampled using Kromekote cards and deposit recoveries were examined on glass plates. Physicochemical properties studied were: viscosity-shear rate relationship, surface tension, volatility, pH, conductance, electrophoretic mobility and zeta potential. Formulations containing low surfactant concentrations provided Newtonian liquids with low viscosities. These liquids atomized into small droplets and provided low recoveries of spray deposits on sampling units. However, formulations containing polymeric adjuvants, and a high concentration of a non-ionic surfactant provided pseudoplastic liquids with high viscosities. These formulations resulted in large droplets with high recoveries of spray deposits on sampling units. Among the physicochemical properties studied, viscosity, surface tension, volatility and electrophoretic mobility, played important roles on liquid atomization and droplet deposition.     

Influence of surfactant concentration on foliar retention of pesticides used in forestry

Abstract

Aqueous tank mixes of permethrin, fenitrothion, Bacillus thuringiensis (B.t.), diflubenzuron (DFB), and glyphosate containing different amounts of Triton® X‐114, a nonionic surfactant, were prepared. Glyphosate formed clear solutions, permethrin and fenitrothion formed emulsions, DFB and B.t provided suspensions. Emulsion stability of permethrin and fenitrothion increased with increasing surfactant level, while the emulsion drop size decreased.

Foliage of white oak, trembling aspen, white spruce and balsam fir were dipped in tank mixes of pesticides (except B.t.) labelled with ¹⁴carbon. The amount of pesticide retained on foliage was determined by liquid scintillation counting. Foliage was also dipped in non‐radioactive B.t. tank mixes, and the protein retained was determined colorimetrically. With all tank mixes, a direct relationship was observed between the mass of liquids retained on foliage and liquid viscosity. In contrast, the amount of pesticide retained was unaffected by viscosity, but was influenced by emulsion drop size. Initially, the amount of pesticide retained on foliage increased with increasing surfactant concentration. Beyond an optimum surfactant level, the emulsion drop sizes were too small and the emulsions became too stable to allow maximum retention of pesticides on foliage. With the glyphosate solutions, however, no optimum surfactant level was indicated because foliar concentrations continued to increase with increasing surfactant levels.     

Sonolytic reactions of phenanthrene in organic extraction solutions

Ultrasonic extraction is a common method used to extract semi-volatile and nonvolatile organic compounds such as polycyclic aromatic hydrocarbons (PAHs) from solid matrices. However, ultrasonic energy has been suspected to lead to undesired reactions of the solute and thus affect qualitative and quantitative results. In this paper, sonolytic reactions of phenanthrene in common organic extraction solutions were examined using a 20 kHz ultrasonic probe under conditions commonly used for ultrasonic extraction. Extraction parameters including phenanthrene concentration, solvent type, pulse length, and sonication time were investigated. Hexane:acetone (1:1 V/V) resulted in less phenanthrene degradation than dichloromethane (DCM):acetone (1:1 V/V). Initial solute concentration, length of sonication time, and solvent type affected the degradation of phenanthrene. Reaction byproducts including methylphenanthrene and methylnaphthalene detected after sonication indicate that phenanthrene reacts by both direct pyrolysis and reaction with methyl or ethyl radicals formed from solvent pyrolysis.     

Influence of adjuvants on physicochemical properties, droplet size spectra and deposit patterns: relevance in pesticide applications

The influence of adjuvants on physicochemical properties, droplet size spectra and deposit patterns of five aqueous spray mixtures was studied under laboratory conditions, using two surfactants, Atlox 3409F and Triton X-114; two humectants, propylene glycol and glycerol; and one polymeric adjuvant, Agrisol FL-100F. For the sake of comparison, two fenitrothion formulations containing polymeric adjuvants, and water were also included in the study. Spray was applied at 25 degrees C and 75 +/- 5% relative humidity, in an enclosure using a twin fluid atomizer. Deposits were collected on Kromekote card/glass plate units. Physicochemical properties studied were: relative viscosity, surface tension, apparent viscosity-shear rate relationship, volatility, pH and conductance. The first four of these properties played significant roles on the droplet and deposit patterns on sampling units. However, the chemical nature of the adjuvants also played some role. Between the two surfactants tested, Triton X-114 provided a pseudoplastic medium, but both surfactant solutions provided similar droplet size spectra and deposit patterns. Between the two humectants, glycerol proved to be more advantageous than propylene glycol. The polymeric adjuvant provided droplet sizes similar to those of the two surfactants, although the recovery of the applied spray volume was higher. Among the two fenitrothion formulations, the one containing lower amounts of polymeric adjuvants showed some advantages, although deposits on the actual biological target should be examined before any definite conclusions can be drawn on the optimum adjuvant concentrations in end-use formulations.     

Endosulfan and diazinon toxicity to the freshwater rotifer Brachionus calyciflorus.

The acute toxicity of endosulfan and diazinon to the freshwater rotifer Brachionus calyciflorus was determined after 24 hours exposure to these toxicants. The mean 24 hr-LC50 values were 5.15 and 29.22 mg/L for endosulfan and diazinon respectively. Based on these results, four sublethal concentrations were chosen to determined the median lethal time (LT50) at each concentration of toxicant tested. We also used a control with the solvent (acetone). The concentration tested were 1/5, 1/4, 1/2 and 2/3th LC50 (24hr) for both pesticides. We found a decrease in the median lethal time (LT50) with increasing pesticide concentrations. The LT50 values ranged from 6.49 to 3.48 days after endosulfan treatment, and from 6.96 to 2.49 days after diazinon exposure. No effects on survival were observed in control animals exposed to the solvent.     

Comparison of the droplet size spectra produced by rotary atomizers and hydraulic nozzles under simulated aerial application conditions

Abstract

A wind tunnel was used to characterize the droplet size spectra of liquid sprays from several different atomizers and nozzles used under simulated aerial application conditions. The atomizers included a D8–46 nozzle, a Through Valve Boom (TVB) nozzle, and rotary cage and drum atomizers.

The D8–46 hydraulic nozzle was evaluated, using water, at orientations of 0, 10, 20, 30, 40, 50, 60, 70, 80 and 90° relative to 145 and 180 km/h airstreams. The TVB nozzle was evaluated using water, water with isopropyl alcohol, and water with a non‐ionic surfactant at airstream velocities between 130 and 180 km/h. The rotary atomizers were evaluated at different rotation rates, flow rates of water and an insecticide, in 130 and 180 km/h airstreams.

The volumetric droplet size spectra parameters (D_vo.x) decreased as the angle of the D8–46 nozzle and the airstream velocity increased. Empirical models were developed to predict these values for different windspeed and nozzle angle conditions. The TVB nozzle produced larger droplets than the other atomizers under similar conditions, with a decrease in the D_vo.x parameter values as the airstream velocity increased.

The D_vo.x parameter values produced by the rotary atomizers increased as the liquid flow rate increased, and as the rotation rate and airstream velocity decreased, and were lower for the insecticide than for water. The slotted rotary drum atomizer gave the best control over droplet size, generally producing mono‐modal droplet size spectra where the other atomizers often produced bi‐ and multimodal spectra.     

The formation of bound residues of diazinon in four UK soils: implications for risk assessment

The behaviour of diazinon in the soil determines the likelihood of further pollution incidents, particularly leaching to water. The most significant processes in the control of the fate of diazinon in the soil are microbial degradation and the formation of bound residues. Soils from four sites in the UK were amended with diazinon and its ¹⁴C labelled analogue and incubated for 100 days. After 0, 10, 21, 50 and 100 days, the formation of bound residues was assessed by solvent extraction, and the microbial degradation of diazinon by mineralisation assay. In microbially active soils, diazinon is degraded rapidly, reducing the risk of future pollution incidents. However, where there was limited mineralisation there was also significantly lower formation of bound residues, which may lead to water pollution via leaching. The formation of bound residues was dependent on extraction type. Acetonitrile extraction identified bound residues in all soils, with the bound residue fraction increasing with increasing incubation time.     

The degradation of chlorpyrifos and diazinon in aqueous solution by ultrasonic irradiation: effect of parameters and degradation pathway

In this paper, elimination of two types of organophosphorus pesticides (OPPs), chlorpyrifos and diazinon spiked in aqueous solution by ultrasonic irradiation was investigated. Results showed that chlorpyrifos and diazinon could be effectively and rapidly degraded by ultrasonic irradiation, and the degradation of both pesticides was strongly influenced by ultrasonic power, temperature and pH value. Furthermore, two and seven products for the degradation of chlorpyrifos and diazinon formed during ultrasonic irradiation have been identified by gas chromatography-mass spectrometry, respectively. The hydrolysis, oxidation, hydroxylation, dehydration and decarboxylation were deduced to contribute to the degradation reaction and the degradation pathway for each pesticide under ultrasonic irradiation was proposed. Finally, the toxicity evaluation indicated that the toxicity decreased for diazinon solution after ultrasonic irradiation, but it increased for chlorpyrifos solution. The detoxification of OPPs by ultrasonic irradiation was discriminative.     

Formation and stability of polychlorinated biphenyl Pickering emulsions

An emulsion stabilized by colloidal suspensions of finely divided solids is known as a Pickering emulsion. The potential for polychlorinated biphenyls (PCBs) to form Pickering emulsions ex situ when in contact with powdered solids, such as clays and metal oxides, is investigated here. Bentonite, iron oxide and magnesium oxide dispersions proved to be robust Pickering emulsion stabilizers, whereas manganese oxide dispersions were not. Batch experiments revealed that emulsions can be formed using a moderately low energy input and can be stabilized with solid concentrations as low as 0.5 wt.%. For the base conditions (volumetric oil fraction (phi(oil))=30 vol.%; solid concentration (chi)=2 wt.%), the formed emulsions were indefinitely stable and the initial average droplet diameters varied from 80 to 258 mum, depending on the solid used in the colloidal dispersion. The average droplet size varied at early time, but for most conditions stabilized to a steady-state value 1 week after preparation. The effect of Ostwald ripening was limited. At greater than 0.5 wt.% concentration, the efficiency of the solid dispersion as a stabilizer was dependant on the volumetric oil fraction but not on the solid concentration. Generally, systems with volumetric oil fractions outside of the 20-70 vol.% range were unstable. The emulsions' droplet stability, average droplet size and size distribution were observed to vary as a function of the amount of energy provided to the system, the volumetric oil fraction, and the concentration of the solid in the aqueous dispersion. It is hypothesized that drilling through fractured rock in the immediate vicinity of dense, non-aqueous phase liquid (DNAPL) PCBs may provide both the energy and solid material necessary to form Pickering emulsions.     

Electrospray Ionization Mass Spectrometry (ESI-MS) monitoring of the photolysis of diazinon in aqueous solution: Degradation route and toxicity of by-products against Artemia salina

The photolytic degradation of diazinon, an organophosphorus pesticide, in aqueous medium under assorted pH values was continuously monitored by direct infusion electrospray ionization mass spectrometry (ESI-MS). The results indicated that the UV radiation was quite efficient in promoting the pesticide degradation at the three pH levels evaluated (5, 7 and 8). The m/z of the most abundant ions observed in the mass spectra (MS), in conjunction with the fragmentation patterns of such ionic species (MS/MS data), made possible the proposition of chemical structures for the main by-products formed. As a result, routes for the photodegradation of diazinon in aqueous solution could thus be suggested. In the assays using Artemia salina (brine shrimp) it was verified that the photodegradation products exhibited much lower toxicity than the primary substrate. Aiming at mimicking the conditions ordinarily found in water treatment plants, an additional series of tests was conducted with a solution containing sodium hypochlorite and diazinon. This solution, when not exposed to UV radiation, exhibited high toxicity against the microorganisms. Under the influence of UV radiation, however, the toxicity rates decreased dramatically. This result is relevant because it points toward the confident application of UV radiation to neutralize the deleterious effects caused by diazinon (and perhaps other organophosphorus pesticides) as well as sodium hypochlorite to the environment.     

City refuse compost and sodium dodecyl sulphate as modifiers of diazinon leaching in soil

The effect of a city refuse compost (CRC) and of an anionic surfactant (sodium dodecyl sulphate (SDS) on the leaching of diazinon (0,0-diethyl 0-2-isopropyl-6-methylpyrimidin-4-yl-phosphorothioate) in the soil was studied using packed soil columns. Breakthrough curves showed the existence of various regimes of pesticide adsorption related to the pesticide and organic material nature and the soil properties. Leaching rate and mass transfer of diazinon decrease following the addition of CRC to the soil and increase after the addition of SDS. The degree of increase or decrease was found to depend strongly on the amendment dose added, especially in the case of SDS. The results afford basic data on which to base the possible use of the organic amendments studied in physicochemical methods designed to prevent the pollution of water by hydrophobic pesticides (immobilization) or to restore soils contaminated by these compounds (leaching).     

Effects of carboxylic acids on nC60 aggregate formation

The discovery that negatively charged aggregates of C₆₀ fullerene (nC₆₀) are stable in water has raised concerns regarding the potential environmental and health effects of these aggregates. In this work, we show that nC₆₀ aggregates produced by extended mixing in the presence of environmentally relevant carboxylic acids (acetic acid, tartaric acid, citric acid) have surface charge and morphologic properties that differ from those produced by extended mixing in water alone. In general, aggregates formed in the presence of these acids have a more negative surface charge and are more homogeneous than those produced in water alone. Carboxylic acid identity, solution pH, and sodium ion concentration, which are all intricately coupled, play an important role in setting the measured surface charge. Comparisons between particle sizes determined by analysis of TEM images and those obtained by dynamic light scattering (DLS) indicate that DLS results require careful evaluation when used to describe nC₆₀ aggregates.     

Pesticide adsorption on a calcareous soil modified with sewage sludge and quaternary alkyl-ammonium cationic surfactants

BACKGROUND, AIM AND SCOPE: Pesticides are often found in soil as a result of their application to control pests. They can be transported on soil particles to surface waters or they can lixiviate and reach other environmental compartments. Soil modification with amendments, such as sewage sludge, and with surfactants, h been proposed to reduce pesticide environmental fate. METHODS: The sorption of atrazine, methidathion and diazinon using the batch technique has been studied on non-modified soil and soil modified with sewage sludge and cationic surfactants, as well as the effect of their addition on soil properties such as organic carbon (OC) content and exchange cations. RESULTS AND DISCUSSION: The OC content of the surfactant modified soils was the highest with the surfactant with the longest hydrocarbon chain (hexadecyltrimethyl ammonium bromide, HDTMA). The results of the OC content run in parallel with the increase in pesticide retention. When the sorption was n malized to soil OC content, the retention induced by addition of HDTMA was still the highest, which is an indication that the organic matter derived from the organic cations is a more effective medium to retain dissolved contaminants, than organic matter from native soil. The addition of sewage sludge to the soil did only result in a slight increase of the soil CEC and, hence, moderately affected the ability of the cationic surfactant to retain the pesticides. CONCLUSIONS: The addition of cationic surfactants to soil would possibly reduce the movement to groundwater of atrazine, methidathion and diazinon. In the case of HDTMA, the decrease in sorption at high surfactant loadings was very slow, being that the surfactant was able to retain the pesticides at concentration values which clearly exceeded the monolayer coverage. RECOMMENDATIONS AND PERSPECTIVES: Contamination by pesticides, which are present in the soil due to their direct input in this medium or to spills or illegal tipping, may be hindered from migration to groundwater by application of a cationic surfactant.     

Evaluation of a Daphnia magna renewal life‐cycle test method with diazinon

Abstract

Acute and chronic toxicity tests with diazinon (diethyl 2‐isopropyl‐6‐methyl‐4‐pyrimidinyl phosphorothionate) were conducted on Daphnia magna. The 24‐hr static LC50 was 0.86 μL.L^‐1. The sublethal effects of 0.05, 0.1, 0.5, 0.75 and 1.0 ngL^‐1 of diazinon concentrations on the survival, reproduction and growth of D. magna were monitored for 21 days. The algae Nannochloris oculata (5 x 10⁵ cellsmL^‐1) was used to feed the daphnids. The parameters used to determined the effect of the pesticide on D. magna were: mean total young per female; mean brood size; days to first brood; intrinsic rate of natural increase (r); growth; and survival. Reproduction as well as survival was significantly reduced at diazinon concentrations of 0.10 ngL^‐1 and higher. The intrinsic rate of natural increase (r) decreased with increasing concentrations of diazinon. Growth, as measured by body length, was depressed significantly at 0.05 ngL^‐1 of diazinon and higher concentrations. The maximum acceptable toxicant concentration (MATC) was calculated. The chronic data was used to formulate an acute/chronic ratio.     

Influence of dispersants on bioconcentration factors of seven organic compounds with different lipophilicities and structures

Seven compounds with different lipophilicities and structures—1,3,5-trichlorobenzene, pentachlorobenzene, acenaphthylene, 1,4-dimethyl-2-(1-methylphenyl)benzene, 4-ethylbiphenyl, 4,4′-dibromobiphenyl, and 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane—were subjected to bioconcentration tests in carp at concentrations below the water solubilities of the compounds in the presence or absence of a dispersant (either an organic solvent or a surfactant). The bioconcentration factors (BCFs) of the compounds were on the order of 10²–10⁴. The BCF values remained in the range of 15–49% for all the compounds, whether or not a dispersant was present, i.e., the BCF values in the presence of an organic solvent or a surfactant at a concentration below the critical micelle concentration were not significantly smaller than the BCF values in the absence of the solvent or surfactant. This result indicates that the dispersants had no influence on the evaluation of the bioconcentration potential of these test substances.     

基于生物表面活性剂的柴油微乳体系构建与性能研究

以生物表面活性剂鼠李糖脂（RL）为表面活性剂,中长碳链正构醇（正丁醇、正戊醇、正己醇、正庚醇及正辛醇）为助表面活性剂,采用滴定法制备RL／柴油／正构醇／水柴油微乳体系,并考察了表面活性剂用量（Km）、助表面活性剂醇的种类及用量（δas）及离子强度对柴油微乳体系最大增溶水量（Wo）的影响,并对不同条件下获得的柴油微乳体系的运动粘度（μ）和表面张力（γ）进行了表征。通过荧光法测得RL在柴油中的临界胶束浓度CMC为7g／L。当生物表面活性剂与柴油的质量比Km为0．02,助表面活性剂选用正庚醇且醇与表面活性剂的质量比δgs为0．1,NaOH溶液质量分数为0．06％时,柴油微乳体系的肛和T较低,形。最大,性能较佳。     

Investigations of the determination and transformations of diazinon and malathion under environmental conditions using gas chromatography coupled with a flame ionisation detector

Degradation of two model insecticides, diazinon and malathion, and their degradation products 2-isopropyl-6-methyl-4-pyrimidinol--IMP (diazinon hydrolysis product) and malaoxon (malathion oxidation product) was compared and studied in the environment. The pesticides and their metabolites were extracted from samples (water, soil, chicory) with ethyl acetate and subsequently the extracts were analyzed by GC/FID. It was shown that hydrolysis is the major process in the degradation of these pesticides in water. In fact, 95% of diazinon was degraded, and only 10% of malathion was oxidised. In soil 30% of diazinon exposed to the sunlight was decomposed by photolysis, whereas in soil left in the darkness no degradation products were observed. In soil left under environmental conditions, 90% of diazinon was degraded and 40% from its initial concentration was transformed into IMP. The concentrations of the pesticides after 21 days on chicory were under maximal allowable concentration, which is 0.5 ppm for malathion and for diazinon. The concentration of malaoxon was more than twice as high as the allowable value, which is for the sum of malathion and malaoxon 3 ppm.     

Dissipation of Phosalone and Diazinon in Fresh and Dried Alfalfa

The objectives of this study were to determine the persistence of phosalone (S-6-chloro-2,3-dihydro-2-oxobenzoxazol-3-ylmethyl O, O-diethyl phosphorodithioate) and diazinon (O,O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate) residues in fresh and baled alfalfa under field conditions. Plots of alfalfa were sprayed with each insecticide. Fresh alfalfa was sampled up to 20 days after treatment, and dried alfalfa was sampled up to 25 weeks after baling. Samples were analyzed for residues using high performance liquid chromatography (HPLC) equipped with a UV detector. The half-lives of diazinon and phosalone in fresh alfalfa were 1.8 and 3.3 days, respectively. In baled alfalfa the half-life of diazinon and phosalone were 2.8 and 16.7 weeks, respectively. No diazinon residues were detected in baled alfalfa, sampled after week 9, although the concentration of phosalone found at week 25 was 5.51 mg/kg.     

Polymer and invert emulsifying oil effects upon droplet size spectra of sprays

Abstract

A series of wind tunnel atomization studies were carried out to investigate the effects of polymer and invert suspension oil “drift control adjuvants” upon the droplet size distribution spectra produced by nozzles typically used in aerial and ground based spraying of pesticides. A D8–46 disc and core was used as a typical aerial application nozzle, and an 8003 fan nozzle was used for the ground based sprayers simulation. The droplet size spectra were evaluated in a wind tunnel using a Malvern 2600 laser particle size analyzer immediately upon mixing and at 15 minutes after re‐circulation through a pumping system. The addition of the polymer‐based adjuvants significantly increased the droplet size spectra parameters of the spray cloud, but all the polymer products showed signs of breakdown of their molecular arrangements in the liquid medium, as a result of agitation. The invert suspension oil adjuvant did not change the droplet size spectra markedly, nor did it show signs of breakdown of the internal liquid structure after re‐circulation.